海洋天然气水合物的类型及特征

根据天然气水合物的产出条件,海洋环境水合物可以分为二类扩散系统水合物和渗漏系统水合物。扩散系统水合物分布广泛,在水合物稳定带内是水-水合物两相共存的热力学平衡体系,游离气仅发育于稳定带之下,在地震剖面上发育有指示水合物底界的强反射面(BSR)。该类水合物含量低,埋藏深。除温度和压力外,水合物的沉淀受甲烷溶解度和扩散速度的控制,并与气体组分、孔隙水盐度、天然气供应和有机碳转化等有关。渗漏系统与断层等通道相伴生,水合物发育于渗漏系统整个水合物稳定带,是水-水合物-游离气三相共存的热力学非平衡体系,水合物的沉淀受动力学控制。该类水合物含量高,埋藏浅,但一般不发育BSR。而且,天然气渗漏活动在海底沉积物和上覆水体中形成了一系列特殊的地质、地球物理、地球化学和特异生物群异常。     

南海东沙海域浅表层柱状沉积物孔隙水地球化学特征及对冷泉流体活动的指示

海底沉积物孔隙水地球化学特征能够快速响应有机质硫酸盐还原作用(OSR)和甲烷缺氧氧化作用(AOM)引起的变化,并记录冷泉渗漏活动的特征。本文对采集自南海东沙海域天然气水合物发育区的重力柱状沉积物孔隙水样品(D17-2015)进行了阴阳离子(SO_4~(2-)、Ca~(2+)、Mg~(2+))、微量元素(Sr~(2+)、Ba~(2+))、溶解无机碳(DIC)及其δ~(13)C_(DIC)等地球化学分析。在深度剖面上硫酸根离子浓度呈直线降低,确定的硫酸盐-甲烷转换带(SMTZ)约为海底下7.0 m,在紧邻SMTZ界面之下的溶解Ba~(2+)浓度突然增加,同时δ~(13)C_(DIC)(-38.8‰)值极端负偏,说明此站位存在强烈的AOM作用。利用反应-运移模型模拟计算获得的硫酸根向下通量为35.3 mmol/(m~2·a)、甲烷向上的通量为30.0 mmol/(m~2·a)、OSR和AOM消耗硫酸盐的相对比例分别约为15%和85%。这些结果表明AOM作用是占主导作用的生物地球化学过程。     

温度对甲烷渗漏背景下自生矿物形成影响的实验

<正>海底冷泉是指来自海底沉积地层的气体以喷涌或渗漏的方式注入海洋中的一种海洋地质现象[1]。冷泉沉积物一般由碳酸盐和硫化物组成,这些自生矿物一方面将渗漏甲烷和海水中的硫转化并固定在海底沉积物中,显著地调控着全球甲烷收支平衡;另一方面,几乎所有的天然气水合物产地均发现有自生碳酸盐和硫化物的存在。因此,自生碳酸盐和硫化物对下伏天然气水合物具有指示作用,是天然气水合物赋存的地球化学找矿标志和含甲烷冷泉流体渗漏的地球化学标志[2]。自生碳酸盐和硫化物的形成与甲烷     

海洋沉积物甲烷厌氧氧化作用(AOM)及其对无机硫循环的影响

甲烷厌氧氧化作用(AOM)在调控全球甲烷收支平衡以及缓解因甲烷引起的温室效应等方面扮演着十分重要的角色,成为近些年来海洋生物地球化学领域的研究热点之一.一般而言,海洋沉积物孔隙水硫酸盐还原主要是通过2种反应途径来完成,即氧化有机质途径和AOM途径.长期以来,与有机质氧化途径相关的硫酸盐还原作用研究已有充分展示,而由AOM驱动的硫酸盐还原及其对自生硫化铁形成与埋藏的重要贡献却被严重低估.侧重从生物地球化学、同位素地球化学等角度,综述近些年来不同环境条件下海洋沉积物AOM作用发生的地球化学证据和AOM对沉积物孔隙水硫酸盐消耗比例的贡献大小及其调控因素.AOM过程产生的H2S会与沉积物中活性铁结合形成自生铁硫化物.与沉积物浅表层条件相比,AOM过程固定的自生铁硫化物不容易发生再氧化,更利于在沉积物中埋藏保存起来.AOM与海洋沉积物硫酸盐还原作用相偶联,由AOM驱动的硫酸盐还原过程对海底自生铁硫化物形成与埋藏的重要贡献不容忽视.该综述有助加深对海洋沉积物AOM作用的认识及其对硫循环的全面理解.     

冷泉自生碳酸盐岩的沉积结构对冷泉活动示踪的初步研究

<正>冷泉是一种富烃类(主要为甲烷)的低温流体,至今仍活跃在世界范围内大陆边缘陆架区和陆坡区的海底[1]。冷泉持续地将沉积物深部的甲烷带至浅部,在合适的低温高压条件下,甲烷与周边的水一同形成天然气水合物[2]。一方面,天然气水合物具有相当可观的能源前景[3],由此冷泉也受到越来越多的关注;另一方面,到达沉积物浅部的甲烷也会在产甲烷菌和硫酸盐还原菌的共同作用下,与下渗海水带来的硫酸盐进行甲烷厌氧氧化反应(AOM),将甲烷和硫酸盐转化为重碳酸根和硫化氢[4]。大量释放的重碳酸根为     

海底天然气渗漏系统微生物作用及冷泉碳酸盐岩的特征

海底天然气渗漏系统是全球海洋环境中广泛分布的自然现象。部分渗漏天然气通过细菌作用转变为二氧化碳,同时海水硫酸盐被还原为硫化氢, 与孔隙水中的钙和铁结合而沉淀冷泉碳酸盐岩。冷泉碳酸盐岩的常见矿物有微晶方解石、文石、白云石和黄铁矿。冷泉碳酸盐岩常发育一些特殊的组构, 如黄铁矿环带结核、溶蚀面、平底晶洞、凝块和向下生长的叠层石组构等。碳酸盐岩特别负的δ13C值指示碳来源于生物成因的甲烷, 而18O富集可能与天然气水合物的分解有关。冷泉碳酸盐岩中黄铁矿的δ34S值低于海水的, 这指示硫来源于微生物还原的海水硫。冷泉碳酸盐岩中的生物标志化合物及其极负的δ13C值指示微生物的生命代谢活动。     

南海神狐海域富Fe碳酸盐岩烟囱矿物学和地球化学的研究

<正>冷泉碳酸盐岩广泛分布在世界各地的主动或被动大陆边缘,它是冷泉区渗漏的甲烷与海水中硫酸根离子发生甲烷厌氧氧化和硫酸盐细菌还原作用的产物,详细记录海底流体的渗漏情况。因此,利用冷泉碳酸盐岩中的矿物组成、元素含量以及C、O、Fe同位素特征示踪碳酸盐的沉淀氧化还原环境、海底流体来源及其流体活动、探讨天然气水合物存在的可能性具有非常重要的作用。南海北部陆坡是天然气水合物发育的理想场所,已发现水合物发育的地质、地球化学和生物证据。2007年,广州海洋地质调查局在神狐海域     

海底冷泉系统硫的生物地球化学过程及其沉积记录研究进展

地球表层甲烷的迁移转化与气候变化、全球碳硫循环、海底生态环境等密切相关。现代海底冷泉是典型的富甲烷环境,冷泉系统中与甲烷厌氧氧化耦合的微生物硫酸盐还原作用(AOM-MSR)是甲烷最主要的消耗方式。该过程导致了孔隙水地球化学特征的变化,并最终以元素含量和同位素异常的形式记录在相应的自生矿物(黄铁矿、碳酸盐、重晶石)等载体中。因此,冷泉系统中硫的生物地球化学过程及其沉积记录的研究为探究甲烷在地球表层环境演化中的角色奠定了基础。本文围绕冷泉系统中硫的生物地球化学过程,综述了其在确定甲烷渗漏通量和识别古冷泉活动(富甲烷环境)等研究中的进展,重点阐述了在这些研究方向中应用"高维"稳定同位素(~(32)S/~(33)S/~(34)S/~(16)O/~(18)O)所取得的突破性成果。目前已经建立了识别地质历史时期富甲烷环境的方法体系,但其在地史研究中的应用尚在起步阶段。同时,未来应开展富甲烷环境中碳硫循环与环境效应具体关联及其沉积记录的深入研究,以期深化对甲烷在调节地球环境和气候变化中的作用等重大科学研究中的认识。     

扬子板块北缘下志留统龙马溪组重晶石结核特征及其成因机制分析

在扬子板块北缘城口明中剖面及巫溪徐家坝剖面下志留统龙马溪组底部的硅质岩、泥岩中发现椭球状重晶石结核。其矿物组成主要为重晶石颗粒与作为"基质"的黄铁矿、粘土矿物和石英。通过重晶石岩石学、矿物学及锶同位素分析表明,重晶石结核形成于早期成岩阶段松软沉积物的孔隙水中。上升洋流带来丰富的营养及富钡物质,表层海水的高初始生产力促使生物繁盛,海水中的钡通过生物作用富集形成生物钡,生物钡(bio-barite)在埋藏过程中的硫酸盐耗竭区(sulfate depleted zones)通过硫酸盐细菌作用(BSR)溶解被激活提供了钡的来源。围岩岩性(黑色泥岩和硅质泥岩)表明重晶石结核形成于缺氧的环境中。上述研究对深入理解早志留世时期扬子板块北缘古海洋环境有一定的启示作用。     

海洋沉积物孔隙水硫酸盐浓度和碳同位素对天然气水合物的指示

硫酸根离子（SO42－）是海洋沉积物孔隙水中的重要组分之一。硫酸盐还原菌利用孔隙水中SO42－作为氧化剂氧化沉积物中有机质或甲烷，造成孔隙水中SO42－离子浓度降代，同时使溶解在孔隙水中CO2的碳同位素组成降低。研究表明，在有天然气水合物出现的地区，强烈的甲烷缺氧氧化作用使孔隙水SO42－浓度急剧下降，表现为海底沉积物中硫酸盐－甲烷界面（SMI）较浅。如布莱克海台区，SMI界面为5.1～23.9m，界面附近深解于孔隙水中CO2的δ13C值低达－39％。笔者发现南海北京海区几个站位具有类似于布莱克海台区的较浅的SMI界面（7.5～17.2m）和极低的δ13C值（－29‰），结合其他地质、地球物理和地球化学证据，推测这些站位处可能赋存有天然气水合物，值得开展进一步详查工作。     

The effect of dissolved barium on biogeochemical processes at cold seeps

A numerical model was applied to investigate and quantify the biogeochemical processes fueled by the expulsion of barium and methane-rich fluids in the sediments of a giant cold-seep area in the Derugin Basin (Sea of Okhotsk). Geochemical profiles of dissolved Ba²⁺, Sr²⁺, Ca²⁺, SO₄²⁻, HS⁻, DIC, I⁻ and of calcium carbonate (CaCO₃) were fitted numerically to constrain the transport processes and the kinetics of biogeochemical reactions. The model results indicate that the anaerobic oxidation of methane (AOM) is the major process proceeding at a depth-integrated rate of 4.9 μmol cm⁻² a⁻¹, followed by calcium carbonate and strontian barite precipitation/dissolution processes having a total depth-integrated rate of 2.1 μmol cm⁻² a⁻¹. At the low seepage rate prevailing at our study site (0.14 cm a⁻¹) all of the rising barium is consumed by precipitation of barite in the sedimentary column and no benthic barium flux is produced. Numerical experiments were run to investigate the response of this diagenetic environment to variations of hydrological and biogeochemical conditions. Our results show that relatively low rates of fluid flow (<∼5 cm a⁻¹) promote the dispersed precipitation of up to 26 wt% of barite and calcium carbonate throughout the uppermost few meters of the sedimentary column. Distinct and persistent events (several hundreds of years long) of more vigorous fluid flow (from 20-110 cm a⁻¹), instead, result in the formation of barite-carbonate crusts near the sediment surface. Competition between barium and methane for sulfate controls the mineralogy of these sediment precipitates such that at low dissolved methane/barium ratios (<4-11) barite precipitation dominates, while at higher methane/barium ratios sulfate availability is limited by AOM and calcium carbonate prevails. When seepage rates exceed 110 cm a⁻¹, barite precipitation occurs at the seafloor and is so rapid that barite chimneys form in the water column. In the Derugin Basin, spectacular barite constructions up to 20 m high, which cover an area of roughly 22 km² and contain in excess of 5 million tons of barite, are built through this process. In these conditions, our model calculates a flux of barium to the water column of at least 20 μmol cm⁻² a⁻¹. We estimate that a minimum of 0.44 × 10⁶ mol a⁻¹ are added to the bottom waters of the Derugin Basin by cold seep processes, likely affecting the barium cycle in the Sea of Okhotsk.     

Cretaceous black shales as active bioreactors: A biogeochemical model for the deep biosphere encountered during ODP Leg 207 (Demerara Rise)

A transport-reaction model was designed to identify the combination and importance of biogeochemical processes operating in four sites drilled during ODP Leg 207 (Demerara Rise, Equatorial Atlantic). Almost 100 Ma after their deposition, deeply buried Cretaceous black shales still act as active bioreactors in great sediment depths and control the biogeochemical reaction network of the whole sediment column. According to a model calibrated at the four drill sites through inverse modeling techniques, methanogenesis could be identified as a key process that dominates not only organic matter degradation but also sulfate availability through the anaerobic oxidation of methane above the black shales. A complete depletion of sulfate within the black shale sequences promotes the remobilization of biogenic barium that reprecipitates as authigenic barite at the top of the sulfate depletion zone. Temporal dynamics of degradation processes caused continuous shifts of the barite precipitation zone during burial, thus inhibiting the formation of an authigenic barite front or causing the dissolution of earlier formed fronts. Major deviations of pore water sulfate profiles from a linear gradient coincide with depths of decelerated or accelerated transport caused by local porosity minima or maxima. Model-determined reaction rates are by far lower than those found in shallower sediments due to the low metabolic activities that are characteristic for the Deep Biosphere. But even after almost 100 Ma, changing organic matter quality still influences the degradation within the black shale sequences, as it is indicated by model results.     

Methane-derived high-Mg calcite submarine cement in Holocene nodules from the Fraser Delta, British Columbia, Canada

Carbonate nodules and slabs in late Holocene shelly terrigenous deposits of the modern Fraser River delta (～49°N) are formed close to the seafloor by precipitation from saline pore waters of mainly fibrous to bladed crystals of high-Mg (～ 10–20 mol% MgCO₃) calcite cement as coalescing isopachous crusts on grains. Previous reports that the cement is low-Mg calcite are not supported by this study. Highly negative δ¹³C values of ? 7 to ? 59‰ for the cements indicate that the bulk of their carbonate carbon was derived from the microbiological degradation of organic matter in the deltaic deposits during shallow burial. In particular, the production of biogenic methane (CH₄) by anaerobic bacterial fermentation, its upward migration, chemical or biological oxidation to CO₂ and neutralization in the near-surface sediment, and diffusion to microenvironments relatively enriched in organic components, are a possible set of conditions influencing the process and sites of carbonate cementation. Methane-derived Mg-calcite appears also to be the major submarine cement in several other modern occurrences of lithified shallow-water terrigenous sands and muds at non-tropical latitudes.     

Geochemical studies of pore fluid in surface sediment on the Daini Atsumi Knoll

We collected sediment samples and pore water samples from the surface sediment on the Daini Atsumi Knoll, and analyzed the sediments for CH₄, C₂H₆, and δ¹³C_CH4, and the pore fluids for CH₄, C₂H₆, δ¹³C_CH4, Cl⁻, SO₄²⁻, δ¹⁸O_H2O, and δD_H2O, respectively. A comparison of the measured concentration and isotopic composition of methane in pore water samples with those in sediment samples revealed that methane was present in the sediment samples at a higher concentration and was isotopically heavier than those in the pore water samples. It suggests that the effect of the release of a sorbed gas bound to organic particles when heated prior to analysis of hydrocarbons was larger than that of the degassing process. A large amount of a sorbed gas would be a significant source of natural gas. Two striking features are the chemical and isotopic composition of the pore water samples taken from the different sites around the Daini Atsumi Knoll. In the KL09, KL10, and KP07 samples, Cl⁻ concentrations in the pore water samples showed depletion to a minimum of 460 mmol/kg, correspond to  17% dilution of seawater, however the latter was not enriched in CH₄. The isotopic compositions of pore water samples suggested the low-Cl⁻ fluids in the pore water were not derived from dissociation of methane hydrate, but were derived from input of meteoric water. In contrast, in the KP05 samples from the north flank of the Daini Atsumi Knoll, pore water were characterized by CH₄ enrichment more than 370 μmol/kg, but not depleted in Cl⁻ concentrations. The observed methane concentration in the KP05 samples is not sufficient for methane hydrate to form in situ, indicating that the existence of methane hydrate in the surface sediment is negligible, as supported by Cl⁻ concentration. Based on the stable carbon isotope ratio of methane in the pore fluid from the KP05 site (δ¹³C_CH4 < − 50‰PDB), methane is thought to be of microbial origin. The pore waters in the surface sediments in the north flank of the Daini Atsumi Knoll were not directly influenced by upward fluid bearing methane of thermogenic origin from a deeper part of the sedimentary layer. However, extremely high methane concentration in the north flank site as compared with the concentration of pore water taken from the normal seafloor suggests that the north flank site is not the normal seafloor. We hypothesize that upward migration of chemically-reduced fluids from a deeper zone of the sedimentary layer reduces chemically-oxidized solutes in the surface sediment. As a consequence methane production replaced sulfate reduction as the microbial metabolism in the reduced environment of the surface sediment.     

Labile barite contents and dissolved barium concentrations on Blake Ridge: New perspectives on barium cycling above gas hydrate systems

Blake Ridge hosts an extensive gas hydrate system where escaping CH₄ is consumed through anaerobic oxidation of methane (AOM) at a sulfate–methane transition (SMT) in shallow sediment. Previous geochemical work on ridge crest sediment has documented Ba fronts above the SMT, and has suggested that these horizons can be used to constrain the evolution of the SMT and AOM over time. We expand on this concept and further test it by determining the labile Ba contents of sediment and the dissolved Ba²⁺ concentrations of pore waters at four ODP sites on Blake Ridge (on the crest at Sites 994, 995 and 997, and on the southern flank at Site 1059). Labile Ba contents are fairly low at all four sites (0.44 and 1.32 mmol/kg), except within 3 m above the SMT at Sites 994, 995 and 997, where they typically exceed 1.24 mmol/kg and can reach 11.3 mmol/kg. These Ba fronts have a diagenetic origin, and SEM analyses show them to be composed of microcrystalline barite. Site 1059 lacks a prominent Ba front. The lowest labile Ba contents generally underlie the Ba fronts and correlate to the base of the SMT. Dissolved Ba²⁺ concentrations are low (< 1–4 μM) from the seafloor to within 2 m above the main Ba front. Below this depth, they rapidly increase at Sites 994, 995, and 1059, reaching peak concentrations (to 57 μM) at the base of the SMT. By contrast, a rapid rise in dissolved Ba²⁺ is not observed at Site 997. Dissolved Ba²⁺ concentrations are only moderately high (10–25 μM) below the SMT at all four sites. Collectively, this information supports a diagenetic model where barite passing into the SMT dissolves, and some of the dissolved Ba²⁺ then migrates up to form an authigenic barite peak. The contrasting signatures at the different sites indicate non-steady-state differences in the overall process. The size of the peaks on the crest of Blake Ridge necessitates that the recycling of Ba across the SMT has been operating at the current sub-bottom depths for > 100 kyr. Thus, CH₄ escaping through the AOM has likely been fairly constant over this time. It is possible that the SMT is currently rising toward the seafloor at Site 1059.     

Barite deposition resulting from phototrophic sulfide-oxidizing bacterial activity

Barite (BaSO₄) deposits generally arise from mixing of soluble barium-containing fluids with sulfate-rich fluids. While the role of biological processes in modulating barium solubility has been shown, no studies have shown that the biological oxidation of sulfide to sulfate leads to barite deposition. Here we present an example of microbially mediated barite deposition in a continental setting. A spring in the Anadarko Basin of southwestern Oklahoma produces water containing abundant barium and sulfide. As emergent water travels down a stream to a nearby creek, sulfate concentration increases from 0.06 mM to 2.2 mM while Ba²⁺ concentration drops from 0.4 mM to less than 7 μM. Stable isotope analysis, microbial activity studies, and in situ experiments provide evidence that as sulfide-rich water flows down the stream, anaerobic, anoxygenic, phototrophic bacteria play a dominant role in oxidizing sulfide to sulfate. Sulfate then precipitates with Ba²⁺ producing barite as travertine, cements, crusts, and accumulations on microbial mats. Our studies suggest that phototrophic sulfide oxidation and concomitant sulfur cycling could prove to be important processes regulating the cycling of barium in continental sulfur-containing systems.     

深圳沿海表层海水与地表水关系的地球化学分析

依据深圳沿海所取31件表层海水样品的水化学数据,对主要离子Ca2+、Mg2+、Na+、K+、SO42-和HCO3-与C l-以及B r-与C l-的关系作散点图分析。西海岸表层海水Ca2+、K+、SO42-和HCO3-与C l-的比偏离海水稀释线,源于其位于珠江河道影响范围,与珠江水有不同程度的混合;东海岸表层海水Ca2+、K+和HCO3-与C l-的比主要围绕海水稀释线波动,表明沿海表层海水流动缓慢,受表层海水蒸发和当地沿岸污染河水排泄的长期累积影响;靠近深圳湾的5件西海岸海水样品成分与东海岸表层海水相似。     

Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ³⁴S versus δ¹⁸O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ³⁴S versus δ¹⁸O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H₂O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.     

论河北丰宁牛圈银（金）矿床的成矿时限问题

南沙海槽的构造和沉积受控于南海的构造运动和加里曼丹西北大陆边缘的演化,具有适于天然气水合物形成的物源基础、温压条件、输导系统和储藏场所。似海底反射层(BSR)出现在水深650~2 800 m、海底下65~350 m深的晚中新世沉积物中,与褶皱、逆冲推覆构造及穹窿构造有关;沉积物中的甲烷含量和孔隙水的SO24-含量表现出异常变化特征,硫酸盐-甲烷界面(SMI)深度仅为8~11 m;表层沉积的自生石膏和黄铁矿的成岩环境与甲烷流体排溢引起的厌氧甲烷氧化(AOM)有关,这些地球物理和地球化学指标均指示南沙海槽发育天然气水合物。研究表明,南沙海槽沉积物的甲烷以二氧化碳还原型微生物成因为主,少量为混合气,海槽东南部可能是最有潜力的天然气水合物远景区。     

The Impact of Sediment and Carbon Fluxes on the Biogeochemistry of Methane and Sulfur in Littoral Baltic Sea Sediments (Himmerfjärden, Sweden)

Three sediment stations in Himmerfjärden estuary (Baltic Sea, Sweden) were sampled in May 2009 and June 2010 to test how low salinity (5–7 ‰), high primary productivity partially induced by nutrient input from an upstream waste water treatment plant, and high overall sedimentation rates impact the sedimentary cycling of methane and sulfur. Rates of sediment accumulation determined using ²¹⁰Pb_excess and ¹³⁷Cs were very high (0.65–0.95 cm?year^?1), as were the corresponding rates of organic matter accumulation (8.9–9.5 mol C?m^?2?year^?1) at all three sites. Dissolved sulfate penetrated <20 cm below the sediment surface. Although measured rates of bicarbonate methanogenesis integrated over 1 m depth were low (0.96–1.09 mol?m^?2?year^?1), methane concentrations increased to >2 mmol?L^?1 below the sulfate–methane transition. A steep gradient of methane through the entire sulfate zone led to upward (diffusive and bio-irrigative) fluxes of 0.32 to 0.78 mol?m^?2?year^?1 methane to the sediment–water interface. Areal rates of sulfate reduction (1.46–1.92 mol?m^?2?year^?1) integrated over the upper 0–14 cm of sediment appeared to be limited by the restricted diffusive supply of sulfate, low bio-irrigation (α?=?2.8–3.1 year^?1), and limited residence time of the sedimentary organic carbon in the sulfate zone. A large fraction of reduced sulfur as pyrite and organic-bound sulfur was buried and thus escaped reoxidation in the surface sediment. The presence of ferrous iron in the pore water (with concentrations up to 110 μM) suggests that iron reduction plays an important role in surface sediments, as well as in sediment layers deep below the sulfate–methane transition. We conclude that high rates of sediment accumulation and shallow sulfate penetration are the master variables for biogeochemistry of methane and sulfur cycling; in particular, they may significantly allow for release of methane into the water column in the Himmerfjärden estuary.